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United States Patent |
5,167,691
|
Maravetz
|
December 1, 1992
|
Herbicidal 5-amino-1-phenyl pyrazole compounds
Abstract
This application discloses herbicidal 1-aryl-pyrazoles, compositions
containing them, methods of preparing them, and methods for controlling
undesired plant growth by preemergent or postemergent application of the
herbicidal compositions to the locus where control is desired. The
herbicidal compounds have the following generic structure:
##STR1##
in which Ar is
##STR2##
R is chlorine, cyano, or nitro; R.sup.1 is a group --C(O)CR.sup.11
R.sup.12 --O--R.sup.13 in which R.sup.11 and R.sup.12 are independently
hydrogen or alkyl; R.sup.13 is hydrogen, alkylcarbonyl, phenylcarbonyl,
phenylmethyl, or alkylaminosulfonyl; R.sup.2 is hydrogen, alkyl,
alkylcarbonyl, alkoxycarbonyl, or a group --C(O)CR.sup.11 R.sup.12
--O--R.sup.13 ; R.sup.3, R.sup.4, R.sup.6, R.sup.7 are independently
hydrogen or halogen; R.sup.5 is halogen or haloalkyl; R.sup.8 is halogen;
R.sup.9 is haloalkyl; R.sup.10 is hydrogen, halogen, or a group
--NR.sup.14 R.sup.15 in which R.sup.14 is hydrogen or alkyl; R.sub.15 is
alkyl, alkynyl, or a group --CHR.sup.16 --Ar.sup.1 in which R.sup.16 is
hydrogen or alkyl; and Ar.sup.1 is tetrahydrofuran-2-yl; furan-2-yl,
thien-2-yl, phenyl, or phenyl substituted with halogen or alkoxy. When
R.sup.10 is a group --NR.sup.14 R.sup.15, in addition to the substituents
listed above, R.sup.1 may be alkylcarbonyl, haloalkylcarbonyl, or
cycloalkylcarbonyl; and R.sup.2 may be hydrogen, alkylcarbonyl, or
cycloalkylcarbonyl.
Inventors:
|
Maravetz; Lester L. (Westfield, NJ)
|
Assignee:
|
FMC Corporation (Philadelphia, PA)
|
Appl. No.:
|
770697 |
Filed:
|
October 3, 1991 |
Current U.S. Class: |
504/282; 504/177; 504/178; 504/181; 504/253; 548/371.7; 548/372.1; 548/372.5 |
Intern'l Class: |
A01N 043/56; A01N 057/16 |
Field of Search: |
548/375,376
71/92
|
References Cited
U.S. Patent Documents
4459150 | Jul., 1984 | Hatton et al. | 71/92.
|
4614533 | Sep., 1986 | Schallner et al. | 71/92.
|
4746354 | Aug., 1988 | Gehring et al. | 71/92.
|
4770693 | Aug., 1988 | Gehring et al. | 71/92.
|
4772310 | Sep., 1988 | Stetter et al. | 71/92.
|
4772312 | Sep., 1988 | Schallner et al. | 71/92.
|
4774254 | Sep., 1988 | Stetter et al. | 514/404.
|
4787930 | Nov., 1988 | Gehring et al. | 71/92.
|
4812165 | Mar., 1989 | Schallner et al. | 71/92.
|
4936892 | Jun., 1990 | Gehring et al. | 71/74.
|
Foreign Patent Documents |
303153A | Feb., 1989 | EP | 71/92.
|
3520327 | Dec., 1986 | DE | 548/362.
|
2123420 | Feb., 1984 | GB | 71/92.
|
2136427 | Sep., 1984 | GB | 71/92.
|
Primary Examiner: Ivy; C. Warren
Assistant Examiner: Northington-Davis; Zinna
Attorney, Agent or Firm: Ertelt; H. Robinson, Kennedy; Robert M.
Claims
I claim:
1. A herbicidal compound of the formula:
##STR24##
in which Ar is selected from:
##STR25##
R is chlorine, cyano, or nitro; R.sup.1 is a group --C(O)CR.sup.11
R.sup.12 --O--R.sup.13 in which R.sup.11 and R.sup.12 are independently
hydrogen or alkyl, and R.sup.13 is hydrogen, alkylcarbonyl,
phenylcarbonyl, phenylmethyl, or alkylaminosulfonyl;
R.sup.2 is hydrogen, alkyl, alkylcarbonyl, alkoxycarbonyl, or a group
--C(O)CR.sup.11 R.sup.12 --O--R.sup.13 ;
R.sup.3, R.sup.4, R.sup.6, R.sup.7 are independently hydrogen or halogen;
R.sup.5 is halogen or haloalkyl;
wherein each alkyl and alkoxy contains 1 to 4 carbon atoms, each cycloalkyl
contains 3-6 carbon atoms, and each alkynyl contains 3-4 carbon atoms.
2. A compound of claim 1 in which R is cyano or nitro, and halogen is
chlorine or fluorine.
3. A compound of claim 2 in which Ar is substituted phenyl, R is nitro,
R.sup.11 and R.sup.12 are hydrogen, R.sup.13 is alkylcarbonyl or
alkylaminosulfonyl, R.sup.2 is hydrogen or alkylcarbonyl, R.sup.3,
R.sup.4, R.sup.6, and R.sup.7 are halogen, and R.sup.5 is haloalkyl.
4. A compound of claim 3 in which R.sup.2 is hydrogen or acetyl, R.sup.3,
R.sup.4, R.sup.6, and R.sup.7 are fluorine, and R.sup.5 is
trifluoromethyl.
5. A compound of claim 4 in which R.sup.13 is acetyl and R.sup.2 is
hydrogen.
6. A compound of claim 4 in which R.sup.13 and R.sup.2 are acetyl.
7. A compound of claim 4 in which R.sup.13 is methylaminosulfonyl and
R.sup.2 is hydrogen.
8. A compound of claim 4 in which R.sup.13 is secbutylaminosulfonyl and
R.sup.2 is hydrogen.
9. An herbicidal composition comprising an herbicidally effective amount of
a compound of claim 1 in admixture with a suitable carrier.
10. A method for controlling undesired plant growth which comprises
applying to the locus where control is desired an herbicidally effective
amount of the composition of claim 9.
Description
This invention pertains to novel herbicidal
1-(substituted-aryl)-5-substituted-carbonylamino-4-substituted-pyrazoles
for weed control in agriculture, horticulture, and other fields in which
it is desired to control unwanted plant growth, such as grassy or
broadleaf plant species. In particular it pertains to
1-(substituted-phenyl)- and
1-(substituted-pyridin-2-yl)-5-substituted-carbonylamino-4-(nitro/cyano/ch
loro)pyrazoles as pre- and postemergence herbicides.
A variety of herbicidal 1-arylpyrazoles have previously been described. For
example, U.S. Pat. No. 4,812,165 describes compounds of the formula
##STR3##
wherein Ar represents an optionally substituted phenyl or pyridyl
(including 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl and
3-chloro-5-trifluoromethylpyridin-2-yl);
R.sup.1 represents hydrogen or nitro;
R.sup.2 represents hydrogen, alkyl or a radical --C(O)--A.sup.1
--(O--A.sup.2).sub.n --Y;
A.sup.1 and A.sup.2 independently represent a divalent alkylene radical;
Y includes hydroxyl, substituted alkoxy, or a radical --O--C(O)--R.sup.3
R.sup.3 includes hydrogen, alkyl, alkoxy, amino, and substituted amino; and
n is 1, 2, 3, or 4.
U.S. Pat. No. 4,614,533 describes compounds of the formula
##STR4##
wherein R.sup.1 includes hydrogen, nitro, halogen;
R.sup.2 is hydrogen or a radical --C(O)R.sup.12
R.sup.3, independently of R.sup.2, is hydrogen, --C(O)R--R.sup.12, or
alkyl;
R.sup.4 -R.sup.8 include hydrogen, halogen, alkyl, and haloalkyl;
R.sup.12 includes alkoxyalkyl and alkylthioalkyl.
U.S. Pat. No. 4,772,312 describes compounds of the formula
##STR5##
wherein R.sup.1 is hydrogen or alkyl;
R.sup.2 includes hydrogen, halogen, nitro;
R.sup.3 is hydrogen or a radical --C(O)R.sup.6 ;
R.sup.4 is a hydrogen, alkyl, or a radical --C(O)R.sup.6 ;
R.sup.6 includes alkoxyalkyl and alkylthioalkyl;
Py is a 2-, 3-, or 4-pyridyl group which is substituted with halogen,
cyano, nitro, alkyl, alkoxy, alkoxycarbonyl, haloalkyl, haloalkoxy, or a
group --S(O).sub.m R.sup.9 where m is 0, 1, or 2; and
R.sup.9 is alkyl, amino, substituted amino, or haloalkyl.
U.S. Pat. No. 4,787,930 describes compounds of the formula
##STR6##
in which R.sup.1 includes hydrogen;
R.sup.2 includes hydrogen, nitro, or halogen;
R.sup.3 is hydrogen, or represents a radical --C(X)R.sup.6 or --S(O).sub.n
R.sup.7 and
R.sup.4 is hydrogen, or alkyl, or represents a radical --C(X)--R.sup.6 or
--S(O).sub.n --R.sup.7, or, in the case where R.sup.3 represents a
--SO.sub.2 --R.sup.7 radical or a --C(O)--C.sub.m F.sub.2m+1 radical, also
represents an inorganic or organic cation bonded in salt form;
wherein
R.sup.6 represents hydrogen, alkyl, alkenyl, alkynyl, halogenoalkyl,
alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl or alkylsulfinylalkyl, or
represents optionally substituted cycloalkyl, optionally substituted aryl,
or represents alkoxy or alkylthio, optionally substituted aryloxy,
optionally substituted arylthio, alkylamino, dialkylamino or optionally
substituted arylamino,
X represents oxygen or sulfur;
n represents the number 0, 1 or 2;
m represents the number 1, 2 or 3; and
R.sup.7 represents alkyl, halogenoalkyl, or optionally substituted aryl;
but wherein, in the case where R.sup.1 and R.sup.3 represent hydrogen and
R.sup.2 represents nitro, R.sup.4 does not simultaneously represent a
propionyl radical.
U.S. Pat. No. 4,770,693 describes compounds of the formula
##STR7##
in which R.sup.1 represents cyano, alkoxycarbonyl, alkenyloxycarbonyl,
alkynyloxycarbonyl, aminocarbonyl, alkylaminocarbonyl,
alkenylaminocarbonyl or alkynylaminocarbonyl;
R.sup.2 represents hydrogen, alkyl, alkenyl, alkynyl, optionally
substituted cycloalkyl, alkoxyalkyl, alkylthioalkyl, halogenoalkyl or
optionally substituted aryl; and
R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7, which are identical or
different, represent hydrogen, halogen, cyano, nitro, alkyl, alkoxy,
alkylsulfonyl, alkoxycarbonyl or radical --(X).sub.n --R.sup.8
wherein
X represents oxygen, sulfur, sulfinyl or sulfonyl,
n represents 0 or 1; and
R.sup.8 represents halogenoalkyl, provided that at least one of the
radicals R.sup.3, R.sup.4, R.sup.5, R.sup.6, and
R.sup.7 represents a radical --(X).sub.n --R.sup.8, but R.sup.1 does not
represent cyano if R.sup.5 represents trifluoromethyl.
German patent application DE 3,520,327-A discloses the following
5-amino-4-cyano-1-pyridylpyrazoles as herbicides:
##STR8##
wherein R.sup.1 and R.sup.2 are hydrogen, optionally substituted alkyl,
alkenyl, alkynyl or cycloalkyl, or CXR.sup.3 ;
X is O or S;
R.sup.3 is hydrogen, alkyl, alkoxy, alkoxyalkyl, alkylthio, alkylthioalkyl,
haloalkyl, alkenyl, alkynyl, optionally substituted cycloalkyl, aryl,
aryloxy, arylthio or arylamino, or mono- or dialkylamino; and
Py is substituted pyridyl, but not 5-nitro-2-pyridyl or
3-chloro-5-trifluoromethyl-2-pyridyl.
Other patents and published patent applications which further define the
state of the art include U.S. Pat. Nos. 4,459,150, 4,746,354, 4,772,310,
4,774,254, and 4,936,892, European Patent 303,153A2, and Great Britain
Patent Applications 2,123,420A and 2,136,427A.
An article by M. Dooley, et al., (Aust. J. Chem., 1989, 42, 747-50)
describes the preparation of 1-(substituted
-phenyl)-5-amino-4-cyanopyrazoles, intermediates in the present case, in a
one-pot reaction between substituted hydrazines, malononitrile, and
triethyl orthoformate. This process is similar to that described in Step A
of Example 1 of this application.
It has now been found that
1-(substituted-aryl)-5-substituted-carbonylamino-4-substituted-pyrazoles
are highly active pre- and postemergence herbicidal compounds. The novel
compounds of this invention differ from the compounds of the prior art
especially in the nature of the substituent on the 5-amino group of the
pyrazole ring.
DETAILED DESCRIPTION OF THE INVENTION
The novel 1-(substituted-aryl)-5-substituted
-carbonylamino-4-substituted-pyrazoles of the present invention are
described by the following generic structure:
##STR9##
wherein Ar is selected from:
##STR10##
R is selected from chlorine, cyano, or nitro; R.sup.1 is a group
--C(O)CR.sup.11 R.sup.12 --O--R.sup.13 in which R.sup.11 and R.sup.12 are
independently hydrogen or alkyl; R.sup.13 is selected from hydrogen,
alkylcarbonyl, phenylcarbonyl, phenylmethyl, or alkylaminosulfonyl;
R.sup.2 is selected from hydrogen, alkyl, alkylcarbonyl, alkoxycarbonyl, or
a group --C(O)CR.sup.11 R.sup.12 --O--R.sup.13 ;
R.sup.3, R.sup.4, R.sup.6, R.sup.7 are independently selected from hydrogen
or halogen;
R.sup.5 is selected from halogen or haloalkyl;
R.sup.8 is halogen;
R.sup.9 is haloalkyl;
R.sup.10 is hydrogen,halogen, or a group --NR.sup.14 R.sup.15 in which
R.sup.14 is selected from hydrogen or alkyl; R.sup.15 is alkyl, alkynyl,
or a group --CHR.sup.16 --Ar.sup.1 in which R.sup.16 is selected from
hydrogen or alkyl; and Ar.sup.1 is selected from tetrahydrofuran-2-yl;
furan-2-yl, thien-2-yl, and phenyl or phenyl substituted with halogen or
alkoxy, and when
R.sup.10 is a group --NR.sup.14 R.sup.15, in addition to the substituents
listed above, R.sup.1 may be alkylcarbonyl, haloalkylcarbonyl, or
cycloalkylcarbonyl; and R.sup.2 may be hydrogen, alkylcarbonyl, or
cycloalkylcarbonyl.
Preferred are those compounds in which each alkyl and alkoxy contains 1 to
4 carbon atoms, each cycloalkyl contains 3-6 carbon atoms, and each
alkynyl contains 3-4 carbon atoms.
The compounds of this invention were prepared by one of the following
routes:
##STR11##
The process for the production of compounds of formula (I) has been
disclosed in U.S. Pat. No. 4,787,930 and in U.S. Pat. No. 4,772,312. The
reaction of (I) with an appropriately substituted acetyl chloride (e.g.,
Cl--R.sup.1 =acetoxyacetyl chloride) and triethylamine in tetrahydrofuran
(THF) yielded a
1-(substituted-aryl)-5-(substituted-methylcarbonyl)amino-4-nitropyrazole
(II).
##STR12##
This alternative method for producing compounds of formula (II) begins with
the reaction of a 5-amino-1-(substituted-aryl)pyrazole of formula (III)
with an appropriately substituted-acetyl chloride and triethylamine in
tetrahydrofuran to produce a 1-(substituted-aryl)
-5-(substituted-methylcarbonyl)aminopyrazole (IV). Subsequent nitration of
(IV) with nitric acid in acetic anhydride and acetic acid produced a
1-(substituted-aryl) -5-(substituted-methylcarbonyl)amino-4-nitropyrazole
of formula (II). In cases where the R.sup.1 group of (II) was
methylcarbonyloxymethylcarbonyl, the compound was treated with sodium
hydroxide in ethanol to yield a
1-(substituted-aryl)-5-hydroxymethylcarbonylamino -4-nitropyrazole (V).
The reaction of (V) with a chloride of an R.sup.13 group (e.g.,
methylaminosulfonyl chloride) yielded a
1-(substituted-aryl)-5-(substituted -oxymethylcarbonyl)amino-4-nitropyrazo
le (VI) (e.g.,
1-(substituted-aryl)-5-methylaminosulfonyloxymethylcarbonylamino-4-nitropy
razole).
##STR13##
An appropriately substituted-arylhydrazine was reacted with
ethoxymethylenemalononitrile in acetic acid and water to produce a
substituted-arylhydrazomethylenemalononitrile (VII). Heating (VII) in 2
-ethoxyethanol yielded a 5-amino-1-(substituted-aryl)-4-cyanopyrazole
(VIII). Treatment of (VIII) with pyridine and acetyl chloride in methylene
chloride produced a
1-(substituted-aryl)-4-cyano-5-bis(methylcarbonyl)aminopyrazole (IX).
Heating (IX) in ethanol and water yielded a
1-(substituted-aryl)-4-cyano-5-methylcarbonylaminopyrazole (X). The
reaction of (X) with an appropriately substituted-acetyl chloride (e.g.,
Cl-R.sup.1 =acetoxyacetyl chloride) and triethylamine in tetrahydrofuran
yielded a
1-(substituted-aryl)-4-cyano-5-(N-methylcarbonyl-N-substituted-methylcarbo
nyl)aminopyrazole (XI).
##STR14##
In cases where the compound of formula (VIII) was
5-amino-1-(3,6-dichloro-5-trifluoromethylpyridin-2-yl)-4-cyanopyrazole
(VIIIa), an --NR.sup.14 R.sup.15 group was added by heating this compound
with an appropriately substituted amine (e.g., benzylamine) in
tetrahydrofuran producing a
5-amino-1-(3-chloro-5-trifluoromethyl-6-substituted
-aminopyridin-2-yl)-4-cyanopyrazole (XII). The reaction of (XII) with an
appropriately substituted-acetyl chloride (e.g., Cl-RI =propionyl
chloride) yielded a
5-substituted-carbonylamino-1-(3-chloro-5-trifluoromethyl
-6-substituted-aminopyridin-2-yl)-4-cyanopyrazole (XIII).
##STR15##
To produce a pyrazole with a chlorine in the 4-position, a compound of
formula (XIV) was treated with sulfuryl chloride in methylene chloride.
This process is disclosed in U.S. Pat. No. 4,787,930. Reaction of (XV)
with an appropriately substituted-acetyl chloride (e.g., acetoxyacetyl
chloride) and triethylamine in tetrahydrofuran yielded a
4-chloro-1-(substituted-aryl)-5-(N-methylcarbonyl-N-substituted-methylcarb
onyl)aminopyrazole (XVI).
Each of these methods of preparation is exemplified below.
EXAMPLE 1
(Method A)
1-(2,3,5,6-Tetrafluoro-4-Trifluoromethylphenyl)
-5-Methylcarbonyloxymethylcarbonylamino-4-Nitropyrazole
(Compound 14)
Step A Ethyl
5-amino-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazole-4-ylcarbox
ylate
To a stirred solution of 15.7 grams (0.634 mole) of
2,3,5,6-tetrafluoro-4-trifluoromethylphenylhydrazine in 40 mL of anhydrous
ethanol was added 10.7 grams (0.634 mole) of ethyl
2-cyano-3-ethoxyacrylate. The reaction mixture was heated at reflux for 21
hours, then cooled, and the solvent was removed by distillation under
reduced pressure, leaving a residue. This residue was suspended in 80 mL
of a 50:50 mixture of diethyl ether/n-pentane. A solid formed and was
removed by filtration to yield 20.4 grams of ethyl
5-amino-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazol-4-ylcarboxy
late, m.p. 166-168.degree. C. The nmr spectrum was consistent with the
proposed structure.
Step B 5-Amino-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazole
A stirred mixture of 18.6 grams (0.500 mole) of ethyl
5-amino-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazole-4-ylcarbox
ylate, 23 mL of water, and 23 mL of sulfuric acid was heated at 130.degree.
C. for six hours. After the reaction mixture was cooled, 75 mL of crushed
ice was added. A solid had formed and was collected by filtration; the
filtrate was saved. This solid was washed with water and diethyl ether,
allowed to dry, and set aside for further purification. To the filtrate
was added an aqueous sodium hydroxide solution until a pH of 9.0 was
obtained. A solid formed and was collected by filtration. This solid was
washed with water and dried to yield 3.8 grams of
5-amino-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazole, m.p.
102.5-104.5.degree. C. The nmr spectrum was consistent with the proposed
structure.
The solid that had been set aside was stirred in 50 mL of water, and the pH
of the mixture was adjusted to 9.0 with an aqueous sodium hydroxide
solution. The aqueous mixture was stirred for ten minutes and then
filtered. The filter cake was washed with water and dried to yield an
additional 4.15 grams of product, m.p. 102.5-104.0.degree. C. The nmr
spectrum was consistent with the proposed structure.
Step C
1-(2,3,5,6-Tetrafluoro-4-trifluoromethylphenyl)-5-methylcarbonylaminopyraz
ole
A mixture of 7.48 grams (0.0250 mole) of
5-amino-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazole, 21.0 mL
of glacial acetic acid, and 3.1 mL of acetic anhydride was stirred at room
temperature for approximately 18 hours. The reaction mixture was poured
into 100 mL of ice-water, forming a white precipitate. This solid was
collected by filtration and washed in succession with dilute acetic acid
and water. The washed solid was dried to yield 8.1 grams of
1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)-5-methylcarbonylaminopyraz
ole, m.p. 103-105.degree. C. The nmr spectrum was consistent with the
proposed structure.
Step D
1-(2,3,5,6-Tetrafluoro-4-trifluoromethylphenyl)-5-methylcarbonylamino-4-ni
tropyrazole
A stirred solution of 7.86 grams (0.0230 mole) of
1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)-5-methylcarbonylaminopyraz
ole in 20 mL of glacial acetic acid was cooled in an ice-water bath. Acetic
anhydride (2.9 mL, 0.031 mole) was added dropwise, and the mixture was
stirred briefly. Concentrated nitric acid (1.05 mL, 0.0245 mole) was added
dropwise, and the reaction mixture was allowed to warm to room temperature
and was stirred for four hours. The mixture was poured into 60 mL of
ice-water and stirred, forming a granular yellow solid. This solid was
collected by filtration and washed with water. The solid was purified by
recrystallization from ethanol and water to yield 5.63 grams of
1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)
-5-methylcarbonylamino-4-nitropyrazole, m.p. 136.5-138.5.degree. C. The
nmr spectrum was consistent with the proposed structure.
Step E
5-Amino-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)-4-nitropyrazole
To a stirred solution of 5.63 grams (0.0146 mole) of
1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)-5-methylcarbonylamino-4-ni
tropyrazole in 21 mL of ethanol was added 12.0 mL (0.0144 mole) of
concentrated hydrochloric acid. The reaction mixture was heated at reflux
for approximately 24 hours, then cooled, and the ethanol was removed by
distillation under reduced pressure, leaving an acidic residue. Water
(10.5 mL) was added to this residue, and the mixture was made basic (pH
9.0) by the slow addition of an aqueous sodium hydroxide solution. The
yellow solid that formed was collected by filtration. This solid was dried
to yield 4.9 grams of 5-amino-1-(2,3,5,6-tetrafluoro-4-trifluoro
-methylphenyl)-4-nitropyrazole, m.p. 121.5-123.0.degree. C. The nmr
spectrum was consistent with the proposed structure.
Step F
1-(2,3,5,6-Tetrafluoro-4-trifluoromethylphenyl)-5-methylcarbonyloxymethylc
arbonylamino -4-nitropyrazole
To a stirred solution of 0.68 gram (0.0020 mole) of
5-amino-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl) -4-nitropyrazole
and 0.42 gram (0.0042 mole) of triethylamine in 20 mL of tetrahydrofuran
was added dropwise a solution of 0.55 gram (0.0040 mole) of acetoxyacetyl
chloride in 8 mL of tetrahydrofuran. The reaction mixture was heated at
reflux for two hours. An additional 0.43 gram of acetoxyacetyl chloride
and 0.22 gram of triethylamine were added, and the mixture was heated at
reflux for 20 minutes. The mixture was cooled and filtered, and the
filtrate was evaporated under reduced pressure, leaving an oil. This oil
was purified by column chromatography on silica gel, eluted with ethyl
acetate/n-hexane (50:50) to yield 0.11 gram of
1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)-5-methylcarbonyloxymethylc
arbonylamino -4-nitropyrazole as a waxy solid, Compound 14 of Table 1. The
nmr spectrum was consistent with the proposed structure.
EXAMPLE 2
(Method B)
1-(2,3,5,6-Tetrafluoro-4-Trifluoromethylphenyl) -
5-Methylaminosulfonyloxymethylcarbonylamino -4-Nitropyrazole
(Compound 21)
Step A 1-(2,3,5,6-Tetrafluoro-4-trifluoromethylphenyl)
-5-methylcarbonyloxymethylcarbonylaminopyrazole
To a cold (0.degree. C.), stirred solution of 7.0 grams (0.0234 mole) of
5-amino-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazole (Example
1, Step B) and 2.76 grams (0.0273 mole) of triethylamine in 45 mL of
tetrahydrofuran was added a solution of 3.54 grams (0.0259 mole) of
acetoxyacetyl chloride in 5 mL of tetrahydrofuran. After the addition was
complete, the reaction mixture was allowed to warm to room temperature.
After the mixture had been stirred for 24 hours, an additional 25 mL of
tetrahydrofuran and 2.66 grams (0.0263 mole) of triethylamine were added.
The reaction mixture was heated at reflux temperature for two hours. While
the mixture was at reflux, triethylamine (1.4 grams, 0.0139 mole) and
acetoxyacetyl chloride (0.89 gram, 0.0065 mole) were added to the mixture.
After an additional hour at reflux the mixture was cooled and filtered.
The solvents were removed by evaporation under reduced pressure, leaving a
brown solid residue. The solid residue was washed in succession with a
mixture of diethyl ether and water and then fresh diethyl ether to yield
6.6 grams of a white solid. A portion of this white solid (4.65 grams) was
added to 100 mL of ethanol and 50 mL of water, stirred, and heated at
reflux for 1.75 hours. The mixture was cooled, and the ethanol was removed
by distillation under reduced pressure. The aqueous residue was extracted
with methylene chloride. The organic extract was washed with water. The
organic phase was dried over anhydrous magnesium sulfate and filtered.
Evaporation of the filtrate under reduced pressure yielded 3.92 grams of
1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)-5-methylcarbonyloxymethyl-
carbonylaminopyrazole as a pale yellow oil. The nmr spectrum was consistent
with the proposed structure.
Step B
1-(2,3,5,6-Tetrafluoro-4-trifluoromethylphenyl)-5-methylcarbonyloxymethylc
arbonylamino -4-nitropyrazole
A mixture of 3.63 grams of
1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)-5-methylcarbonyloxymethylc
arbonylaminopyrazole, 0.5 mL of concentrated nitric acid, and 1.53 grams
(0.0150 mole) of acetic anhydride in 9.4 mL of glacial acetic acid was
stirred at room temperature for two hours. This mixture was poured into
ice-water, forming a yellow solid. This solid was collected by filtration
and was dried to yield 3.50 grams of
1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)-5-methylcarbonyloxymethylc
arbonylamino-4-nitropyrazole. The nmr spectrum was consistent with the
proposed structure.
Step C
1-(2,3,5,6-Tetrafluoro-4-trifluoromethylphenyl)-5-hydroxymethylcarbonylami
no-4-nitropyrazole
A mixture of 1.5 grams (0.0034 mole) of
1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)-5-methylcarbonyloxymethylc
arbonylamino -4-nitropyrazole, 2.63 mL of a 2N aqueous sodium hydroxide
solution, 1.5 mL of ethanol, and 4.7 mL of water was stirred at room
temperature for 15 minutes. After the pH was adjusted to 5.0 with dilute
hydrochloric acid, ethanol was removed from the mixture by distillation
under reduced pressure. The remaining aqueous phase was extracted with
methylene chloride, and the extract was washed with water. The washed
organic phase was dried over anhydrous magnesium sulfate and filtered. The
filtrate was evaporated under reduced pressure to yield 0.75 gram of
1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)-5
-hydroxymethylcarbonylamino-4-nitropyrazole as a solid (compound 19 of
Table 1). The nmr spectrum was consistent with the proposed structure.
Step D
1-(2,3,5,6-Tetrafluoro-4-trifluoromethylphenyl)-5-methylaminosulfonyloxyme
thylcarbonylamino-4-nitropyrazole
A stirred solution of 0.48 gram (0.0012 mole) of
1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)-5-hydroxymethylcarbonylami
no-4-nitropyrazole and 0.27 gram (0.0027 mole) of triethylamine in 28.5 mL
of methylene chloride was cooled in an ice-water bath. Methylaminosulfonyl
chloride (0.55 gram, 0.0043 mole) was added dropwise, and the mixture was
allowed to warm to room temperature and stir for four hours. The reaction
mixture was filtered to remove a salt that had formed. The filtrate was
extracted in succession with water, dilute hydrochloric acid, a saturated,
aqueous sodium bicarbonate solution, and water. The organic phase was
dried over anhydrous magnesium sulfate and filtered. The filtrate was
evaporated under reduced pressure, leaving a brown oil. This oil was
purified by column chromatography on silica gel, which was eluted with
ethyl acetate: n-heptane (1:1) to yield an oil. This oil crystallized in
methylene chloride and n-heptane to yield 0.07 gram of
1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)-5-methylaminosulfonyloxyme
thylcarbonylamino -4-nitropyrazole as an ivory-colored solid (Compound 21
of Table 1). The nmr spectrum was consistent with the proposed structure.
EXAMPLE 3
(Method C)
1-(3-Chloro-5-Trifluoromethylpyridin-2-YL)-4-Cyano-5-(N-Methylcarbonyl-N-Me
thylcarbonyloxymethylcarbonyl) -Aminopyrazole
(Compound 26)
Step A (3-Chloro-5-trifluoromethylpyridin-2-yl)
-hydrazomethylenemalononitrile
To a stirred solution of 12.2 grams (0.100 mole) of
ethoxymethylenemalononitrile in 80 mL of water and 160 mL of glacial
acetic acid was added 21.2 grams (0.100 mole) of
(3-chloro-5-trifluoromethylpyridin-2-yl)hydrazine. The reaction mixture
was stirred briskly to dissolve the hydrazine, resulting in a clear, red
solution. On stirring at room temperature for five hours, this solution
formed a thick slurry, which was diluted with 600 mL of water and
filtered. The filter cake was washed with water and dried to yield 20.0
grams of
(3-chloro-5-trifluoromethylpyridin-2-yl)hydrazomethylenemalononitrile. The
nmr spectrum was consistent with the proposed structure.
Step B 5-Amino-1-(3-chloro-5-trifluoromethylpyridin-2-yl)-4-cyanopyrazole
A stirred solution of 19.0 grams (0.066 mole) of
(3-chloro-5-trifluoromethylpyridin-2-yl)hydrazomethylenemalononitrile in
190 mL of 2-ethoxyethanol was heated at reflux for four hours. The
reaction mixture was cooled and was poured into 600 mL of water. The
resulting aqueous slurry was stirred for a brief period and then filtered.
The filter cake was washed with water and dried to yield 18.4 grams of
5-amino-1-(3-chloro-5 -trifluoromethylpyridin-2-yl)-4-cyanopyrazole. The
nmr spectrum was consistent with the proposed structure.
Step C
1-(3-Chloro-5-trifluoromethylpyridin-2-yl)-4-cyano-5-bis(methylcarbonyl)am
inopyrazole
Under a dry nitrogen atmosphere, a stirred mixture of 5.02 grams (0.0175
mole) of
5-amino-1-(3-chloro-5-trifluoromethylpyridin-2-yl)-4-cyanopyrazole and
12.7 grams (0.161 mole) of pyridine in 470 mL of methylene chloride was
cooled to 5.degree. C. Acetyl chloride (12.5 grams, 0.159 mole) was added
dropwise. After the addition was complete, the reaction mixture was heated
at reflux for approximately 20 hours. The mixture was then cooled, treated
with decolorizing charcoal, and filtered through a pad of Celite.RTM.
filter aid. The filtrate was evaporated under reduced pressure, leaving a
residue. This residue was stirred vigorously with a mixture of water and
diethyl ether. The diethyl ether was allowed to evaporate at room
temperature and pressure, leaving an aqueous slurry, which was cooled in
an ice bath and then filtered. The filter cake was washed with water and
air dried to yield 6.6 grams of
1-(3-chloro-5-trifluoromethylpyridin-2-yl)-4-cyano-5-bis(methylcarbonyl)am
inopyrazole, m.p. 129.5-132.degree. C. The nmr spectrum was consistent with
the proposed structure.
Step D
1-(3-Chloro-5-trifluoromethylpyridin-2-yl)-4-cyano-5-methylcarbonylaminopy
razole
A stirred mixture of 0.32 gram (8.6.times.10.sup.-4 mole) of
1-(3-chloro-5-trifluoromethylpyridin-2-yl)-4-cyano-5-bis-
(methylcarbonyl)aminopyrazole, 10 mL of water, and 10 mL of ethanol was
heated at reflux for four hours.
The mixture was cooled, and most of the ethanol was removed by distillation
under reduced pressure. The aqueous pot residue, which contained a solid,
was diluted with water, and the mixture was filtered. The filter cake was
dried to yield 0.22 gram of 1-(3-chloro
-5-trifluoromethylpyridin-2-yl)-4-cyano-5-methylcarbonylaminopyrazole. The
nmr spectrum was consistent with the proposed structure.
Step E
1-(3-Chloro-5-trifluoromethylpyridin-2-yl)-4-cyano-(N-methylcarbonyl-N-met
hylcarbonyloxymethylcarbonyl)aminopyrazole
A stirred solution of 0.22 gram (6.7.times.10.sup.-4 mole) of
1-(3-chloro-5-trifluoromethylpyridin-2-yl)-4-cyano-5-methylcarbonylaminopy
razole and 0.081 gram (8.0.times.10.sup.-4 mole) of triethylamine in 25 mL
of tetrahydrofuran was cooled to -5.degree. C. Acetoxyacetyl chloride
(0.10 gram, 7.3.times.10.sup.-4 mole) was added, and the mixture was
allowed to warm to room temperature. The reaction mixture was heated at
reflux for 30 minutes and then cooled to 0.degree. C. Additional
acetoxyacetyl chloride (0.05 gram) and triethylamine (0.04 gram) were
added, and the mixture was heated at reflux for 30 minutes. The mixture
was cooled and filtered. The filtrate was evaporated under reduced
pressure, leaving a residue, which was diluted with water and stirred,
forming a waxy solid. This solid was recrystallized from ethanol and water
to yield 0.15 gram of 1-(3-chloro-5-trifluoromethylpyridin-2-yl)
-4-cyano-5-(N-methylcarbonyl-N-methylcarbonyloxymethylcarbonyl)aminopyrazo
le, m.p. 170-173.degree. C. (Compound 26 of Table 1). The nmr spectrum was
consistent with the proposed structure.
EXAMPLE 4
(Method D)
1-(3-Chloro-5-Trifluoromethyl-6-Phenylmethylaminopyridin
-2-YL)-4-Cyano-5-Ethylcarbonylaminopyrazole
(Compound 53)
Step A 3,6-Dichloro-5-trifluoromethylpyridin-2-ylhydrazine
To a stirred mixture of 127.0 grams (0.507 mole) of
2,3,6-trichloro-5-trifluoromethylpyridine and 62.0 grams (0.632 mole) of
potassium acetate in 470 mL of ethanol was added dropwise 17.9 grams
(0.557 mole) of anhydrous hydrazine. During the addition the reaction
temperature rose to 55.degree. C., and a yellow slurry formed. This
mixture was stirred at room temperature for approximately sixteen hours
and then diluted with two liters of diethyl ether and shaken. The
resultant mixture was filtered, and the filtrate was evaporated under
reduced pressure, leaving a solid residue. This solid was purified by
crystallization from 445 mL of methanol and 235 mL of water to yield,
after drying, 91.5 grams of
3,6-dichloro-5-trifluoromethylpyridin-2-ylhydrazine. The nmr spectrum was
consistent with the proposed structure.
Step B 3,6-Dichloro-5-trifluoromethylpyridin-2-yl
-hydrazomethylenemalononitrile
To a stirred mixture of 30.0 grams (0.246 mole) of
ethoxymethylenemalononitrile in 186 mL of water and 370 mL of glacial
acetic acid was added 60.0 grams (0.244 mole) of
3,6-dichloro-5-trifluoromethylpyridin-2-ylhydrazine. After stirring for
four hours at room temperature this mixture was a clear, wine-red
solution, which was stirred for an additional 20 hours. A small sample of
the reaction solution, on dilution with water, formed an oily resin, from
which the supernatant liquid was decanted. When the resin was stirred with
a small portion of chloroform, a granular, yellow solid formed. When this
solid was added to the reaction solution, a precipitate formed. This
mixture was stirred for 30 minutes and then poured into 1600 mL of water.
This aqueous mixture was stirred occasionally with a glass rod during a
one hour period. The aqueous mixture was filtered, the filter cake washed
with water and air-dried to yield 45.1 grams of
3,6-dichloro-5-trifluoromethylpyridin -2-ylhydrazomethylenemalononitrile,
m.p. 144-147.degree. C. The nmr spectrum was consistent with the proposed
structure.
Step C 5-Amino-1-(3,6-dichloro-5-trifluoromethylpyridin
-2-yl)-4-cyanopyrazole
A stirred solution of 45.1 grams (0.140 mole) of
3,6-dichloro-5-trifluoromethylpyridin-2-ylhydrazomethylenemalononitrile in
300 mL of 2-ethoxyethanol was heated at reflux for approximately 1.5
hours. The solvent was removed by distillation under reduced pressure,
leaving a slurry-like residue. This residue was washed twice with 300 to
400 mL portions of n-pentane. The resultant solid was dried to yield 38.6
grams of
5-amino-1-(3,6-dichloro-5-trifluoromethylpyridin-2-yl)-4-cyanopyrazole.
The nmr spectrum was consistent with the proposed structure.
Step D 5-Amino-1-(3-chloro-5-trifluoromethyl-6-phenylmethylaminopyridin
-2-yl)-4-cyanopyrazole
A stirred solution of 6.0 grams (0.019 mole) of 5
-amino-1-(3,6-dichloro-5-trifluoromethylpyridin-2-yl)-4-cyanopyrazole and
15.4 grams (0.144 mole) of benzylamine in 100 mL of tetrahydrofuran was
heated at reflux for 3.5 hours. The reaction mixture was cooled and
filtered. The filtrate was evaporated under reduced pressure, leaving a
residue. This residue was dissolved in methylene chloride, and the organic
solution was washed in succession with water, dilute hydrochloric acid,
and water. The washed organic phase was dried over anhydrous magnesium
sulfate and filtered. The filtrate was evaporated under reduced pressure,
leaving a pale yellow solid residue. This residue, in 200 mL of petroleum
ether, was heated to reflux and then allowed to cool to room temperature.
The mixture was filtered, and the filter cake was dried to yield 3.0 grams
of 5-amino-1-(3-chloro-5-trifluoromethyl-6-phenylmethylaminopyridin
-2-yl)-4-cyanopyrazole. The nmr spectrum was consistent with the proposed
structure.
Step E
1-(3-Chloro-5-trifluoromethyl-6-phenylmethylaminopyridin-2-yl)-4-cyano-5-e
thylcarbonylaminopyrazole
A stirred solution of 0.5 gram (0.001 mole) of
5-amino-1-(3-chloro-5-trifluoromethyl-6-phenylmethylaminopyridin-2-yl)-4-c
yanopyrazole and 1.0 gram (0.013 mole) of pyridine in 25 mL of methylene
chloride was cooled to -10.degree. C. A solution of 1.2 grams (0.013 mole)
of propionyl chloride in 10 mL of methylene chloride was added dropwise.
After completion of the addition, the reaction mixture was allowed to warm
to room temperature and then was heated at reflux for approximately 19
hours. The reaction mixture was cooled and evaporated under reduced
pressure, leaving an oil. This oil was partitioned between diethyl ether
and water. The organic phase was washed in succession with water, dilute
hydrochloric acid, and water. The washed organic phase was evaporated
under reduced pressure, leaving a residue. This residue was dissolved in
13 mL of ethanol and 13 mL of water. The resultant mixture was stirred and
heated at reflux. Potassium carbonate (0.20 gram, 0.0014 mole) was added,
and the mixture was stirred and heated at reflux for approximately 15
minutes. The solvents were removed by distillation under reduced pressure,
leaving a waxy solid. This solid was purified by crystallization from
ethanol and water to yield 0.51 gram of
1-(3-chloro-5-trifluoromethyl-6-phenylmethylaminopyridin-2-yl)-4-cyano-5-e
thylcarbonylaminopyrazole, m.p. 139-142.degree. C. (Compound 53 of Table
1). The nmr spectrum was consistent with the proposed structure.
EXAMPLE 5
(Method E)
4-Chloro-1-(2,3,5,6-Tetrafluoro-4-Trifluoromethylphenyl)
-5-(N-Methylcarbonyl-N-Methylcarbonyloxymethylcarbonyl)aminopyrazole
(Compound 1)
Step A 4-Chloro-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)
-5-methylcarbonylaminopyrazole
A solution of 0.80 gram (0.0023 mole) of
1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)-5-methylcarbonylaminopyraz
ole (Step C of Example 1) in 25 mL of methylene chloride was cooled to
-5.degree. C. Sulfuryl chloride (9.35 gram, 0.0026 mole) was added
dropwise during a two minute period. After the addition was complete, the
reaction mixture was allowed to warm to room temperature and was stirred
for 1.5 hours. The reaction mixture was diluted with methylene chloride
and washed in succession with an aqueous, saturated sodium bicarbonate
solution and water. The organic phase was evaporated under reduced
pressure to yield 0.82 gram of
4-chloro-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)
-5-methylcarbonylaminopyrazole as a white solid, m.p. 45-47.degree. C. The
nmr spectrum was consistent with the proposed structure.
Step B 4-Chloro-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)
-5-(N-methylcarbonyl-N-methylcarbonyloxymethylcarbonyl)aminopyrazole
A stirred solution of 0.50 gram (0.0013 mole) of
4-chloro-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)
-5-methylcarbonylaminopyrazole and 0.6 mL of triethylamine in 15 mL of
tetrahydrofuran was cooled to -5.degree. C. Acetoxyacetyl chloride (0.55
gram, 0.0040 mole) was added, and the mixture was allowed to warm to room
temperature. The reaction mixture was filtered, and the filtrate was
evaporated under reduced pressure, leaving a residue. This residue was
dissolved in methylene chloride and washed with water. The organic phase
was dried over anhydrous magnesium sulfate and filtered. The filtrate was
evaporated under reduced pressure, leaving a gummy solid. This solid was
stirred in a small portion of ethanol to yield a white solid. This mixture
was filtered, and the filter cake was dried to yield 0.29 gram of
4-chloro-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)-5-(N-methylcarbon
yl-N-methylcarbonyloxymethylcarbonyl)aminopyrazole (Compound 1 of Table 1).
The nmr spectrum was consistent with the proposed structure.
Representative compounds of the invention prepared by the methods
exemplified above are shown in Table 1.
Characterizing properties of these compounds are given in Table 2.
HERBICIDAL ACTIVITY
The 1-(substituted-aryl)-5-substituted-carbonylamino
-4-substituted-pyrazoles of this invention were tested in pre- and
postemergence evaluations using a variety of broadleaf and grasseous crops
and weeds. The test species used in demonstrating the herbicidal activity
of this invention include cotton (Gossypium hirsutum var. DPL61), soybean
(Glycine max var. Williams), field corn (Zea mays var. Agway 425X), rice
(Oryza sativa var. Labelle), wheat (Triticum aestivum var. Wheaton),
morningglory (Ipomea lacunosa or Ipomea hederacea), wild mustard (Brassica
kaber), velvetleaf (Abutilon theophrasti), barnyardgrass (Echinochloa
crusgalli), green foxtail (Setaria viridis), johnsongrass (Sorghum
halepense), blackgrass (Alopecurus myosuroides), common chickweed
(Stellaria media), and common cocklebur (Xanthium pennsylvanicum).
Preparation of Flats
Preemergence:
Two disposable fiber flats (8 cm.times.15 cm.times.25 cm) for each rate of
application for each candidate herbicide are filled to an approximate
depth of 6.5 cm with steam-sterilized sandy loam soil. The soil is leveled
and impressed with a template to provide five or six evenly spaced furrows
13 cm long and 0.5 cm deep in each flat.
In one case, seeds of cotton, soybean, corn, rice, and wheat are planted in
the furrows of the first flat, and seeds of morningglory, wild mustard,
velvetleaf, barnyardgrass, green foxtail, and johnsongrass are planted in
the furrows of the second flat. The six-row template is employed to firmly
press the seeds into place. A topping soil of equal portions of sand and
sandy loam soil is placed uniformly on top of each flat to a depth of
approximately 0.5 cm.
In another case, seeds of soybean, wheat, corn, green foxtail, and
johnsongrass are planted in the furrows of the first flat, and seeds of
velvetleaf, morningglory, common chickweed, cocklebur, and blackgrass are
planted in the furrows of the second flat. The five-row template is
employed to firmly press the seeds into place. A topping soil of equal
portions of sand and sandy loam soil is placed uniformly on top of each
flat to a depth of approximately 0.5 cm.
In each case, the flats are first watered, then sprayed with a solution of
test compound as described below.
Postemergence:
Two flats for each rate of application for each herbicide candidate are
also prepared for postemergence application. The postemergence flats are
prepared in the same manner as discussed above for the preemergence flats.
The prepared flats are watered for 8-11 days, then the foliage of the
emerged tests plants is sprayed with a solution of test compound as
described below. Application of Herbicides
In both the preemergence and postemergence tests, the candidate herbicides
are applied as aqueous acetone solutions, usually at rates equivalent to
8.0 kilograms/hectare (kg/ha) and/or submultiples thereof, i.e., 4.0
kg/ha, 2.0 kg/ha, and so on.
The four flats (2 preemergence, 2 postemergence) are placed together and
sprayed with 30 mL of test solution containing an appropriate amount of
the test compound, i.e., approximately 7.5 mL of the test solution is
sprayed on each of the four flats. Preemergence applications are made as
sprays to the soil surface. Postemergence applications are made as sprays
to the foliage. After treatment, the two preemergence flats are watered
regularly at the soil surface for approximately 2 weeks, at which time
phytotoxicity data are recorded. In the postemergence test the foliage is
kept dry for 24 hours after treatment, then watered regularly for
approximately 2 weeks, and phytotoxicity data recorded.
Preparation of Test Solutions
For flats of the size described above, an application rate of 8.0 kg/ha of
active ingredient is equivalent to 0.06 g of active ingredient/flat (0.24
g for the four flats). A stock solution of 0.48 g of the candidate
herbicide in 60 mL of a 50:50 mixture of water and acetone containing 0.5%
(v/v) of sorbitan monolaurate emulsifier/solubilizer is divided into two
30 mL portions, each containing 0.24 g of the candidate herbicide. For the
8.0 kg/ha application, one of the 30 mL portions is sprayed undiluted onto
the four flats (7.5 mL/flat). The remaining 30 mL portion of the stock
solution is diluted with an additional 30 mL of the aqueous
acetone/emulsifier mixture to provide 60 mL of a solution containing 0.24
g of candidate herbicide. As above, this solution is divided into two 30
mL portions, each containing 0.12 g of candidate herbicide. One of the 30
mL portions is applied, without further dilution, to the four flats for
the 4 0 kg/ha rate. The remaining 30 mL portion is further diluted with an
equal amount of aqueous acetone/emulsifier mixture, and the resulting 60
mL solution of 0.12 g candidate herbicide is divided into two 30 mL
portions each containing 0.06 g of candidate herbicide. One of the 30 mL
(0.06 g active) portions is used for the 2.0 kg/ha application rate and
the other is used in the preparation of lower rate test solutions by the
same serial dilution technique.
Phytotoxicity data are taken as percent control. Percent control is
determined by a method similar to the 0 to 100 rating system disclosed in
"Research Methods in Weed Science," 2nd ed., B. Truelove, Ed.; Southern
Weed Science Society; Auburn University, Auburn, Ala., 1977. The rating
system is as follows:
______________________________________
Herbicide Rating System
Rating Description
Percent
of Main Crop Weed
Control
Categories Description Description
______________________________________
0 No effect No crop No weed
reduction control
or injury
10 Slight Slight dis- Very poor weed
effect coloration control
or stunting
20 Some dis- Poor weed
coloration, control
stunting or
stand loss
30 Crop injury Poor to defi-
more pronounced
cient weed
but not lasting
control
40 Moderate Moderate injury,
Deficient weed
effect crop usually control
recovers
50 Crop injury Deficient to
more lasting,
moderate weed
recovery doubtful
control
60 Lasting crop Moderate weed
injury, no control
recovery
70 Severe Heavy injury and
Control some-
stand loss what less than
satisfactory
80 Crop nearly des-
Satisfactory
troyed, a few
to good weed
survivors control
90 Only occasional
Very good to
live plants left
excellent
control
100 Complete Complete crop
Complete weed
effect destruction destruction
______________________________________
For herbicidal application, the active compounds are formulated into
herbicidal compositions by admixture in herbicidally effective amounts
with adjuvants and carriers normally employed in the art for facilitating
the dispersion of active ingredients for the particular utility desired,
recognizing the fact that the formulation and mode of application of a
toxicant may affect the activity of the material in a given application.
Thus, for agricultural use the present herbicidal compounds may be
formulated as granules of relatively large particle size, as water-soluble
or water-dispersible granules, as powdery dusts, as wettable powders, as
emulsifiable concentrates, as solutions, or as any of several other known
types of formulations, depending on the desired mode of application.
These herbicidal compositions may be applied either as water-diluted
sprays, or dusts, or granules to the areas in which suppression of
vegetation is desired. These formulations may contain as little as 0.1%,
0.2% or 0.5% to as much as 95% or more by weight of active ingredient.
Dusts are free flowing admixtures of the active ingredient with finely
divided solids such as talc, natural clays, kieselguhr, flours such as
walnut shell and cottonseed flours, and other organic and inorganic solids
which act as dispersants and carriers for the toxicant; these finely
divided solids have an average particle size of less than about 50
microns. A typical dust formulation useful herein is one containing 1.0
part or less of the herbicidal compound and 99.0 parts of talc.
Wettable powders, also useful formulations for both pre- and postemergence
herbicides, are in the form of finely divided particles which disperse
readily in water or other dispersant. The wettable powder is ultimately
applied to the soil either as a dry dust or as an emulsion in water or
other liquid. Typical carriers for wettable powders include Fuller's
earth, kaolin clays, silicas, and other highly absorbent, readily wet
inorganic diluents. Wettable powders normally are prepared to contain
about 5-80% of active ingredient, depending on the absorbency of the
carrier, and usually also contain a small amount of a wetting, dispersing
or emulsifying agent to facilitate dispersion. For example, a useful
wettable powder formulation contains 80.8 parts of the herbicidal compound
17.9 parts of Palmetto clay, and 1.0 part of sodium lignosulfonate and 0.3
part of sulfonated aliphatic polyester as wetting agents. Frequently
additional wetting agent and/or oil will be added to the tank mix for
postemergence application to facilitate dispersion on the foliage and
absorption by the plant.
Other useful formulations for herbicidal applications are emulsifiable
concentrates (ECs) which are homogeneous liquid or paste compositions
dispersible in water or other dispersant, and may consist entirely of the
herbicidal compound and a liquid or solid emulsifying agent, or may also
contain a liquid carrier, such as xylene, heavy aromatic naphthas,
isophorone, or other non-volatile organic solvent. For herbicidal
application these concentrates are dispersed in water or other liquid
carrier, and normally applied as a spray to the area to be treated. The
percentage by weight of the essential active ingredient may vary according
to the manner in which the composition is to be applied, but in general
comprises 0.5 to 95% of active ingredient by weight of the herbicidal
composition.
Flowable formulations are similar to ECs except that the active ingredient
is suspended in a liquid carrier, generally water. Flowables, like ECs,
may include a small amount of a surfactant, and contain active ingredient
in the range of 0.5 to 95%, frequently from 10 to 50%, by weight of the
composition. For application, flowables may be diluted in water or other
liquid vehicle, and are normally applied as a spray to the area to be
treated.
Typical wetting, dispersing or emulsifying agents used in agricultural
formulations include, but are not limited to, the alkyl and alkylaryl
sulfonates and sulfates and their sodium salts; alkylaryl polyether
alcohols; sulfated higher alcohols; polyethylene oxides; sulfonated animal
and vegetable oils; sulfonated petroleum oils; fatty acid esters of
polyhydric alcohols and the ethylene oxide addition products of such
esters; and the addition product of long-chain mercaptans and ethylene
oxide. Many other types of useful surface-active agents are available in
commerce. The surface-active agent, when used, normally comprises from 1
to 15% by weight of the composition.
Other useful formulations include suspensions of the active ingredient in a
relatively non-volatile solvent such as water, corn oil, kerosene,
propylene glycol, or other suitable solvents.
Still other useful formulations for herbicidal applications include simple
solutions of the active ingredient in a solvent in which it is completely
soluble at the desired concentration, such as acetone, alkylated
naphthalenes, xylene, or other organic solvents. Granular formulations,
wherein the toxicant is carried on relatively coarse particles, are of
particular utility for aerial distribution or for penetration of cover
crop canopy. Pressurized sprays, typically aerosols wherein the active
ingredient is dispersed in finely divided form as a result of vaporization
of a low boiling dispersant solvent carrier, such as the Freon fluorinated
hydrocarbons, may also be used. Water-soluble or water-dispersible
granules are also useful formulations for herbicidal application of the
present compounds. Such granular formulations are free-flowing, non-dusty,
and readily water-soluble or water-miscible. The soluble or dispersible
granular formulations described in U.S. Pat. No. 3,920,442 are useful
herein with the present herbicidal compounds. In use by the farmer on the
field, the granular formulations, emulsifiable concentrates, flowable
concentrates, solutions, etc., may be diluted with water to give a
concentration of active ingredient in the range of say 0.1% or 0.2% to
1.5% or 2%.
The active herbicidal compounds of this invention may be formulated and/or
applied with insecticides, fungicides, nematicides, plant growth
regulators, fertilizers, or other agricultural chemicals and may be used
as effective soil sterilants as well as selective herbicides in
agriculture. In applying an active compound of this invention, whether
formulated alone or with other agricultural chemicals, an effective amount
and concentration of the active compound is of course employed; the amount
may be as low as, e.g. about 1 to 250 g/ha, preferably about 4 to 30 g/ha.
For field use, where there are losses of herbicide, higher application
rates (e.g., four times the rates mentioned above) may be employed.
The active herbicidal compounds of this invention may be used in
combination with other herbicides, e.g. they may be mixed with, say, an
equal or larger amount of a known herbicide such as chloroacetanilide
herbicides such as
2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide (alachlor),
2-chloro-N-(2 -ethyl-6-methylphenyl-N-(2-methoxy-1-methylethyl)acetamide
(metolachlor), and N-chloroacetyl-N-(2,6-diethylphenyl)glycine
(diethatyl-ethyl); benzothiadiazinone herbicides such as
3-(1-methylethyl)-(1H)-2,1,3-benzothiadiazin-4-(3H)-one-2,2-dioxide
(bentazon); triazine herbicides such as 6-chloro-N-ethyl-N-(1-methylethyl)
-1,3,5-triazine-2,4-diamine (atrazine), and 2-[4-chloro
-6-(ethylamino)-1,3,5-triazin-2-yl]amino-2-methylpropanenitrile
(cyanazine); dinitroaniline herbicides such as
2,6-dinitro-N,N-dipropyl-4-(trifluoromethyl)benzeneamine (trifluralin);
aryl urea herbicides such as N'-(3,4-dichlorophenyl)-N,N-dimethylurea
(diuron) and N,N -dimethyl-N'-[3-(trifluoromethyl)phenyl]urea
(fluometuron); and
2-[(2-chlorophenyl)methyl]-4,4-dimethyl-3-isoxazolidinone.
It is apparent that various modifications may be made in the formulation
and application of the compounds of this invention without departing from
the inventive concepts herein as defined in the claims.
TABLE 1
__________________________________________________________________________
##STR16##
Compound
R R.sup.1 R.sup.2 R.sup.3
R.sup.4
R.sup.5
R.sup.6
R.sup.7
__________________________________________________________________________
1 Cl C(O)CH.sub.2 OC(O)CH.sub.3
C(O)CH.sub.3
F F CF.sub.3
F F
2 CN C(O)CH.sub.2 OC(O)CH.sub.3
C(O)CH.sub.2 OC(O)CH.sub.3
H H CF.sub.3
H H
3 CN C(O)CH.sub.2 OC(O)CH.sub.3
H H H CF.sub.3
H H
4 CN C(O)CH.sub.2 OC(O)CH.sub.3
C(O)C.sub.2 H.sub.5
Cl
Cl
Cl H H
5 CN C(O)CH.sub.2 OC(O)CH.sub.3
H F F CF.sub.3
F F
6 NO.sub.2
C(O)CH.sub.2 OH H Cl
H CF.sub.3
H H
7 NO.sub.2
C(O)CH.sub.2 OC(O)CH.sub.3
H Cl
H CF.sub.3
H H
8 NO.sub.2
C(O)CH.sub.2 OH H Cl
H CF.sub.3
H Cl
9 NO.sub.2
C(O)CH.sub.2 OC(O)CH.sub.3
H Cl
H CF.sub.3
H Cl
10 NO.sub.2
C(O)CH.sub.2 OSO.sub.2 NHCH.sub.3
H Cl
H CF.sub.3
H Cl
11 NO.sub.2
C(O)CH.sub.2 OSO.sub.2 NHCH(CH.sub.3).sub.2
H Cl
H CF.sub.3
H Cl
12 NO.sub.2
C(O)CH.sub.2 OH H F F CF.sub.3
F F
13 NO.sub.2
C(O)CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5
H F F CF.sub.3
F F
14 NO.sub.2
C(O)CH.sub.2 OC(O)CH.sub.3
H F F CF.sub.3
F F
15 NO.sub.2
C(O)C(CH.sub.3).sub.2 OC(O)CH.sub.3
H F F CF.sub.3
F F
16 NO.sub.2
C(O)CH.sub.2 OC(O)C.sub.6 H.sub.5
H F F CF.sub.3
F F
17 NO.sub.2
C(O)CH.sub.2 OC(O)CH.sub.3
C(O)CH.sub.2 OC(O)CH.sub.3
F F CF.sub.3
F F
18 NO.sub.2
C(O)CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5
C(O)CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5
F F CF.sub.3
F F
19 NO.sub.2
C(O)CH.sub.2 OC(O)CH.sub.3
C(O)CH.sub.3
F F CF.sub.3
F F
20 NO.sub.2
C(O)CH.sub.2 OC(O)CH.sub.3
C(O)OCH.sub.3
F F CF.sub.3
F F
21 NO.sub.2
C(O)CH.sub.2 OSO.sub.2 NHCH.sub.3
H F F CF.sub.3
F F
22 NO.sub.2
C(O)CH.sub.2 OSO.sub.2 NHC.sub.2 H.sub.5
H F F CF.sub.3
F F
23 NO.sub.2
C(O)CH.sub.2 OSO.sub.2 NHCH(CH.sub.3)C.sub.2 H.sub.5
H F F CF.sub.3
F F
__________________________________________________________________________
##STR17##
Compound
R R.sup.1 R.sup.2 R.sup.8
R.sup.9
R.sup.10
__________________________________________________________________________
24 CN C(O)CH.sub.2 OC(O)CH.sub.3
H Cl CF.sub.3
H
25 CN C(O)CH.sub.2 OC(O)CH.sub.3
CH.sub.3 Cl CF.sub.3
H
26 CN C(O)CH.sub.2 OC(O)CH.sub.3
C(O)CH.sub.3
Cl CF.sub.3
H
27 CN C(O)CH.sub.2 OC(O)CH.sub.3
C(O)CH.sub.2 OC(O)CH.sub.3
Cl CF.sub.3
H
28 CN C(O)CH.sub.2 OC(O)CH.sub.3
H Cl CF.sub.3
Cl
29 CN C(O)CH.sub.2 OC(O)CH.sub.3
C(O)CH.sub.3
Cl CF.sub.3
Cl
30 CN C(O)CH.sub.2 OCH.sub. 3
H Cl CF.sub.3
NHCH.sub.2 C.sub.6 H.sub.5
31 NO.sub.2
C(O)CH.sub.2 OH
H Cl CF.sub.3
H
32 NO.sub.2
C(O)CH.sub.2 OC(O)CH.sub.3
H Cl CF.sub.3
H
33 NO.sub.2
C(O)CH.sub.2 OC(O)CH.sub.3
C(O)CH.sub.3
Cl CF.sub.3
H
34 NO.sub.2
C(O)CH.sub.2 OC(O)CH.sub.3
C(O)CH.sub.2 OC(O)CH.sub.3
Cl CF.sub.3
H
35 NO.sub.2
C(O)CH.sub.2 OC(O)CH.sub.3
H Cl CF.sub.3
Cl
36 CN C(O)CH.sub.3
H Cl CF.sub.3
NHCH.sub.3
37 CN C(O)CH.sub.3
C(O)CH.sub.3
Cl CF.sub.3
NHCH.sub.3
38 CN C(O)CH.sub.3
H Cl CF.sub.3
N(C.sub.3 H.sub.7).sub.2
39 CN C(O)CH.sub.3
H Cl CF.sub.3
NHCH.sub.2 CCH
40 CN C(O)CH.sub.3
H Cl CF.sub.3
N(CH.sub.3)CH.sub.2 CCH
41 CN C(O)C.sub.2 H.sub.5
H Cl CF.sub.3
N(CH.sub.3)CH.sub.2 CCH
42 CN C(O)CH.sub.3
C(O)CH.sub.3
Cl CF.sub.3
NHCH.sub.2 CCH
43 CN C(O)CH.sub.3
C(O)CH.sub.3
Cl CF.sub.3
N(CH.sub.3)CH.sub.2 CCH
44 CN C(O)CH.sub.3
H Cl CF.sub.3
NHCH.sub.2 C.sub.6 H.sub.5
45 CN C(O)CH.sub.3
C(O)CH.sub.3
Cl CF.sub.3
NHCH.sub.2 C.sub.6 H.sub.5
46 CN C(O)CH.sub.2 Cl
H Cl CF.sub.3
NHCH.sub.2 C.sub.6 H.sub.5
47 CN C(O)CH.sub.3
H Cl CF.sub.3
NHCH(CH.sub.3)C.sub.6 H.sub.5
48 CN C(O)CH.sub.3
C(O)CH.sub.3
Cl CF.sub.3
NHCH(CH.sub.3)C.sub.6 H.sub.5
49 CN C(O)CH.sub.3
H Cl CF.sub.3
NHCH.sub.2 C.sub.6 H.sub.4 -4-Cl
50 CN C(O)CH.sub.3
C(O)CH.sub.3
Cl CF.sub.3
NHCH.sub.2 C.sub.6 H.sub.4 -4-Cl
51 CN C(O)CH.sub.3
H Cl CF.sub.3
NHCH.sub.2 C.sub.6 H.sub.4 -4-OCH.su
b.3
52 CN C(O)CH.sub.3
C(O)CH.sub.3
Cl CF.sub.3
NHCH.sub.2 C.sub.6 H.sub.4 -4-OCH.su
b.3
53 CN C(O)C.sub.2 H.sub.5
H Cl CF.sub.3
NHCH.sub.2 C.sub.6 H.sub.5
54 CN C(O)C.sub.2 H.sub.5
H Cl CF.sub.3
N(CH.sub.3)CH.sub.2 C.sub.6
H.sub.5
55 CN C(O)C.sub. 2 H.sub.5
C(O)C.sub.2 H.sub.5
Cl CF.sub.3
N(CH.sub.3)CH.sub.2 C.sub.6
H.sub.5
56 CN C(O)C.sub.2 H.sub.5
H Cl CF.sub.3
NHCH.sub.2 C.sub.6 H.sub.4 -4-Cl
57 CN C(O)C.sub.2 H.sub.5
C(O)C.sub.2 H.sub.5
Cl CF.sub.3
NHCH.sub.2 C.sub.6 H.sub.4 -4-Cl
58 CN C(O)C.sub.3 H.sub.7
H Cl CF.sub.3
NHCH.sub.2 C.sub.6 H.sub.5
59 CN C(O)C.sub.3 H.sub.7
C(O)C.sub.3 H.sub.7
Cl CF.sub.3
NHCH.sub.2 C.sub.6 H.sub.5
60 CN C(O)CH(CH.sub.3).sub.2
H Cl CF.sub.3
NHCH.sub.2 C.sub.6 H.sub.5
61 CN C(O)-cyclopropyl
H Cl CF.sub.3
NHCH.sub.2 C.sub.6 H.sub.5
62 CN C(O)-cyclopropyl
C(O)-cyclopropyl
Cl CF.sub.3
NHCH.sub.2 C.sub.6 H.sub.5
63 CN C(O)CH.sub.3
H Cl CF.sub.3
##STR18##
64 CN C(O)CH.sub.3
C(O)CH.sub.3
Cl CF.sub.3
##STR19##
65 CN C(O)C.sub.2 H.sub.5
H Cl CF.sub.3
##STR20##
66 CN C(O)C.sub.2 H.sub.5
H Cl CF.sub.3
##STR21##
67 CN C(O)C.sub.2 H.sub.5
H Cl CF.sub.3
##STR22##
68 CN C(O)C.sub.2 H.sub.5
C(O)C.sub.2 H.sub.5
Cl CF.sub.3
##STR23##
__________________________________________________________________________
TABLE 2
______________________________________
Characterizing Properties
Compound
No. M.P. (.degree.C.)
______________________________________
1 122-123 24 solid 47 solid
2 121-123 25 solid 48 oil
3 119-123 26 170-173
49 76 (dec)
4 132-134 27 solid 50 62 (dec)
5 176-178 28 solid 51 solid
6 49-51 29 167-170
52 waxy solid
7 oil 30 149-151.5
53 139-142
8 157-160 31 67-70 54 solid
9 oil 32 119-121
55 175-176.5
10 solid 33 solid 56 oil
11 oil 34 solid 57 126-128
12 solid 35 148-151
58 128-131
13 oil 36 181.5-183.5
59 solid
14 waxy solid
37 153-156
60 solid
15 oil 38 oil 61 166-167.5
16 solid 39 154-156
62 oil
17 98-100 40 152-154
63 solid
18 oil 41 solid 64 154-156
19 159-160 42 Waxy solid
65 oil
20 141-142 43 oil 66 oil
21 solid 44 158- 160
67 solid
22 91-95 45 138-143
68 oil
23 solid 46 waxy solid
______________________________________
TABLE 3
______________________________________
PREEMERGENCE HERBICIDAL ACTIVITY (% Control)
Compound No.
1 2 3 4
Rate (kg/ha)
Species 0.5 2.0 0.5 0.5
______________________________________
Velvetleaf 100 60 85 100
Blackgrass 80 50 50 100
Soybean 30 5 10 95
Morningglory 95 80 70 100
Green foxtail
95 30 70 100
Johnsongrass 85 50 70 100
Chickweed 10 10 15 100
Wheat 85 20 30 100
Cocklebur 90 50 50 95
Corn 95 60 80 95
______________________________________
Compound No.
5 6 7 8
Rate (kg/ha)
Species 0.5 0.5 0.5 0.5
______________________________________
Velvetleaf 100 100 100 100
Blackgrass 80 85 85 95
Soybean 50 90 70 95
Morningglory 90 100 100 100
Green foxtail
100 100 100 100
Johnsongrass 90 100 100 100
Chickweed 70 100 100 100
Wheat 70 90 85 95
Cocklebur 95 90 85 100
Corn 100 100 100 100
______________________________________
Compound No.
9 10 11 12
Rate (kg/ha)
Species 0.5 0.5 0.25
0.5
______________________________________
Velvetleaf 100 100 100 100
Blackgrass 95 100 85 95
Soybean 100 100 80 85
Morningglory 100 100 100 100
Green foxtail
100 100 100 100
Johnsongrass 100 100 100 95
Chickweed 100 100 95 95
Wheat 95 100 95 90
Cocklebur 95 100 85 100
Corn 95 100 100 95
______________________________________
Compound No.
13 14 15 16
Rate (kg/ha)
Species 0.5 0.5 0.5 0.5
______________________________________
Velvetleaf 100 100 100 100
Blackgrass 85 100 95 95
Soybean 80 70 70 85
Morningglory 95 100 100 100
Green foxtail
95 95 100 100
Johnsongrass 95 95 95 95
Chickweed 95 100 95 100
Wheat 80 95 85 95
Cocklebur 100 100 95 100
Corn 95 95 95 95
______________________________________
Compound No.
17 18 19 20
Rate (kg/ha)
Species 0.5 0.5 0.5 0.5
______________________________________
Velvetleaf 100 100 100 100
Blackgrass 90 85 100 95
Soybean 40 40 85 40
Morningglory 100 100 100 100
Green foxtail
100 95 100 100
Johnsongrass 95 95 100 95
Chickweed 95 95 100 80
Wheat 70 80 90 85
Cocklebur 100 100 100 100
Corn 95 95 95 95
______________________________________
Compound No.
21 22 23 24
Rate (kg/ha)
Species 0.5 0.5 0.5 0.5
______________________________________
Velvetleaf 100 100 100 95
Blackgrass 95 100 90 45
Soybean 90 85 30 85
Morningglory 100 100 100 100
Green foxtail
100 100 100 100
Johnsongrass 100 100 95 95
Chickweed 100 100 100 95
Wheat 95 95 90 70
Cocklebur 100 100 85 95
Corn 95 95 95 100
______________________________________
Compound No.
25 26 27 28
Rate (kg/ha)
Species 0.5 0.5 0.5 0.5
______________________________________
Velvetleaf 80 100 100 100
Blackgrass 50 100 100 85
Soybean 40 100 95 25
Morningglory 95 100 100 55
Green foxtail
90 100 100 95
Johnsongrass 90 100 100 95
Chickweed 40 100 100 80
Wheat 80 100 100 35
Cocklebur 50 100 95 50
Corn 95 100 100 95
______________________________________
Compound No.
29 30 31 32
Rate (kg/ha)
Species 0.5 1.0 0.5 0.5
______________________________________
Velvetleaf 100 100 100 100
Barnyardgrass 90
Blackgrass 95 100 100
Soybean 15 30 100 100
Morningglory 95 100 100 100
Green foxtail
100 100 100 100
Johnsongrass 95 90 100 100
Chickweed 100 100 100
Wheat 70 90 100 100
Cocklebur 80 95 95
Corn 95 85 100 100
Cotton 100
Rice 70
Wild mustard 100
______________________________________
Compound No.
33 34 35 36
Rate (kg/ha)
Species 0.5 0.5 0.5 2.0
______________________________________
Velvetleaf 100 95 90 100
Barnyardgrass 100
Blackgrass 100 40 70
Soybean 100 55 0 100
Morningglory 100 100 85 100
Green foxtail
100 100 100 100
Johnsongrass 100 90 95 100
Chickweed 100 95 90
Wheat 100 95 50 100
Cocklebur 95 95 0
Corn 100 100 90 100
Cotton 100
Rice 100
Wild mustard 100
______________________________________
Compound No.
37 38 39 40
Rate (kg/ha)
Species 2.0 1.0 1.0 1.0
______________________________________
Velvetleaf 100 100 100 100
Barnyardgrass
100 95 100 100
Soybean 100 60 100 100
Morningglory 100 100 100 100
Green foxtail
100 100 100 100
Johnsongrass 100 100 100 100
Wheat 100 100 100 100
Corn 100 95 100 100
Cotton 100 90 100 100
Rice 95 95 100 95
Wild mustard 100 100 100 100
______________________________________
Compound No.
41 42 43 44
Rate (kg/ha)
Species 1.0 1.0 1.0 2.0
______________________________________
Velvetleaf 100 100 100 100
Barnyardgrass
100 100 95 100
Soybean 100 100 100 100
Morningglory 100 100 100 100
Green foxtail
100 100 100 100
Johnsongrass 100 100 100 100
Wheat 95 100 100 100
Corn 100 100 100 100
Cotton 95 100 100 100
Rice 100 100 95 100
Wild mustard 100 100 100 100
______________________________________
Compound No.
45 46 47 48
Rate (kg/ha)
Species 2.0 1.0 1.0 1.0
______________________________________
Velvetleaf 100 100 100 100
Barnyardgrass
100 95 100 95
Soybean 100 70 5 5
Morningglory 100 100 80 95
Green foxtail
100 100 100 100
Johnsongrass 100 100 100 100
Wheat 100 70 40 40
Corn 100 70 95 80
Cotton 100 90 70 60
Rice 95 60 70 70
Wild mustard 100 100 100 100
______________________________________
Compound No.
49 50 51 52
Rate (kg/ha)
Species 1.0 1.0 1.0 1.0
______________________________________
Velvetleaf 100 100 100 100
Barnyardgrass
85 100 100 90
Soybean 80 80 90 70
Morningglory 95 100 100 100
Green foxtail
100 100 100 100
Johnsongrass 95 100 100 70
Wheat 90 85 95 70
Corn 90 90 95 95
Cotton 95 90 95 90
Rice 95 95 95 95
Wild mustard 100 100 100 100
______________________________________
Compound No.
53 54 55 56
Rate (kg/ha)
Species 1.0 1.0 1.0 1.0
______________________________________
Velvetleaf 100 100 100 100
Barnyardgrass
95 95 100 100
Soybean 100 100 95 85
Morningglory 100 100 100 90
Green foxtail
100 100 100 100
Johnsongrass 95 95 100 100
Wheat 95 85 95 90
Corn 95 95 100 95
Cotton 100 100 95 95
Rice 95 95 95 95
Wild mustard 100 100 100 100
______________________________________
Compound No.
57 58 59 60
Rate (kg/ha)
Species 1.0 1.0 1.0 1.0
______________________________________
Velvetleaf 100 100 100 100
Barnyardgrass
10 100 95 100
Soybean 40 95 100 100
Morningglory 70 100 100 100
Green foxtail
90 100 100 100
Johnsongrass 30 100 100 100
Wheat 15 95 85 95
Corn 15 95 100 100
Cotton 50 95 85 90
Rice 20 85 80 95
Wild mustard 100 100 100 100
______________________________________
Compound No.
61 62 63 64
Rate (kg/ha)
Species 1.0 1.0 1.0 1.0
______________________________________
Velvetleaf 100 100 100 100
Barnyardgrass
100 100 100 100
Soybean 100 100 100 100
Morningglory 100 100 100 100
Green foxtail
100 100 100 100
Johnsongrass 100 100 100 100
Wheat 90 80 100 100
Corn 95 85 100 100
Cotton 85 90 90 100
Rice 95 95 100 100
Wild mustard 100 100 100 100
______________________________________
Compound No.
65 66 67 68
Rate (kg/ha)
Species 1.0 0.5 1.0 1.0
______________________________________
Velvetleaf 100 100 100 100
Barnyardgrass
100 100 100 100
Soybean 100 100 95 100
Morningglory 100 100 100 100
Green foxtail
100 100 100 100
Johnsongrass 100 100 100 100
Wheat 95 100 99 100
Corn 100 100 100 100
Cotton 100 100 100 100
Rice 95 100 100 100
Wild mustard 100 100 100 100
______________________________________
TABLE 4
______________________________________
POSTEMERGENCE HERBICIDAL ACTIVITY (% Control)
Compound No.
1 2 3 4
Rate (kg/ha)
Species 0.5 2.0 2.0 0.5
______________________________________
Velvetleaf 90 40 60 100
Blackgrass 15 40 50 95
Soybean 70 50 40 95
Morningglory 85 60 50 100
Green foxtail
100 70 80 95
Johnsongrass 70 30 20 95
Chickweed 20 40 40 100
Wheat 20 40 40 95
Cocklebur 90 15 15 100
Corn 30 50 60 95
______________________________________
Compound No.
5 6 7 8
Rate (kg/ha)
Species 0.5 0.5 0.5 0.5
______________________________________
Velvetleaf 100 70 80 95
Blackgrass 40 15 50 70
Soybean 70 95 95 95
Morningglory 100 80 95 95
Green foxtail
100 90 85 100
Johnsongrass 90 100 90 95
Chickweed 50 90 95 100
Wheat 70 70 30 50
Cocklebur 100 60 70 90
Corn 95 95 85 80
______________________________________
Compound No.
9 10 11 12
Rate (kg/ha)
Species 0.5 0.5 0.25
0.5
______________________________________
Velvetleaf 100 100 95 100
Blackgrass 70 95 85 95
Soybean 95 100 95 80
Morningglory 100 90 95 100
Green foxtail
100 100 100 100
Johnsongrass 95 100 85 95
Chickweed 100 100 100 100
Wheat 60 95 80 70
Cocklebur 90 100 100 100
Corn 90 100 85 95
______________________________________
Compound No.
13 14 15 16
Rate (kg/ha)
Species 0.5 0.5 0.5 0.5
______________________________________
Velvetleaf 95 100 90 100
Blackgrass 85 100 85 85
Soybean 95 90 60 85
Morningglory 100 100 100 100
Green foxtail
100 100 95 100
Johnsongrass 95 100 90 95
Chickweed 100 100 90 90
Wheat -- 90 40 --
Cocklebur 100 100 90 100
Corn 95 95 80 95
______________________________________
Compound No.
17 18 19 20
Rate (kg/ha)
Species 0.5 0.5 0.5 0.5
______________________________________
Velvetleaf 100 85 100 100
Blackgrass 90 80 95 85
Soybean 80 95 80 95
Morningglory 100 100 100 100
Green foxtail
100 100 100 100
Johnsongrass 95 95 100 100
Chickweed 100 100 95 90
Wheat 100 -- 80 60
Cocklebur 100 95 100 100
Corn 100 95 95 85
______________________________________
Compound No.
21 22 23 24
Rate (kg/ha)
Species 0.5 0.5 0.5 0.5
______________________________________
Velvetleaf 100 100 100 100
Blackgrass 100 100 80 10
Soybean 95 95 95 85
Morningglory 100 100 100 100
Green foxtail
100 100 100 95
Johnsongrass 100 100 100 60
Chickweed 100 100 100 95
Wheat 90 85 80 20
Cocklebur 100 100 95 95
Corn 95 100 95 40
______________________________________
Compound No.
25 26 27 28
Rate (kg/ha)
Species 0.5 0.5 0.5 0.5
______________________________________
Velvetleaf 30 100 100 100
Blackgrass 15 95 100 20
Soybean 70 100 95 25
Morningglory 95 100 100 85
Green foxtail
20 100 100 95
Johnsongrass 40 95 100 90
Chickweed 10 100 100 95
Wheat 10 95 90 0
Cocklebur 40 100 95 40
Corn 60 95 85 35
______________________________________
Compound No.
29 30 31 32
Rate (kg/ha)
Species 0.5 1.0 0.5 0.5
______________________________________
Velvetleaf 100 100 100 100
Barnyardgrass 90
Blackgrass 90 85 95
Soybean 60 70 95 95
Morningglory 95 100 100 100
Green foxtail
100 100 100 100
Johnsongrass 100 -- 100 100
Chickweed 100 100 100
Wheat 15 70 95 100
Cocklebur 70 95 95
Corn 90 60 95 100
Cotton 85
Rice 30
Wild mustard 50
______________________________________
Compound No.
33 34 35 36
Rate (kg/ha)
Species 0.5 0.5 0.5 2.0
______________________________________
Velvetleaf 100 90 80 100
Barnyardgrass 100
Blackgrass 100 0 50
Soybean 100 85 80 100
Morningglory 100 90 95 100
Green foxtail
100 95 100 100
Johnsongrass 100 45 100 100
Chickweed 100 95 95
Wheat 95 10 20 100
Cocklebur 95 80 60
Corn 95 10 70 100
Cotton 100
Rice 100
Wild mustard 100
______________________________________
Compound No.
37 38 39 40
Rate (kg/ha)
Species 2.0 1.0 1.0 1.0
______________________________________
Velvetleaf 100 100 100 100
Barnyardgrass
100 70 95 100
Soybean 100 90 100 95
Morningglory 100 95 100 100
Green foxtail
100 95 100 100
Johnsongrass 100 90 -- 100
Wheat 100 85 100 100
Corn 100 90 100 100
Cotton 100 95 100 100
Rice 100 80 85 95
Wild mustard 100 70 95 100
______________________________________
Compound No.
41 42 43 44
Rate (kg/ha)
Species 1.0 1.0 1.0 2.0
______________________________________
Velvetleaf 100 100 100 100
Barnyardgrass
100 100 100 100
Soybean 95 100 95 100
Morningglory 100 100 100 100
Green foxtail
95 95 100 100
Johnsongrass 95 -- 100 100
Wheat 100 95 100 100
Corn 100 90 100 100
Cotton 100 100 100 100
Rice 100 85 95 100
Wild mustard 95 95 100 95
______________________________________
Compound No.
45 46 47 48
Rate (kg/ha)
Species 2.0 1.0 1.0 1.0
______________________________________
Velvetleaf 100 100 95 90
Barnyardgrass
100 95 100 100
Soybean 100 40 70 60
Morningglory 100 100 95 80
Green foxtail
100 95 90 95
Johnsongrass 100 -- 100 100
Wheat 100 50 70 50
Corn 100 70 70 70
Cotton 100 50 95 100
Rice 100 60 70 30
Wild mustard 100 80 80 95
______________________________________
Compound No.
49 50 51 52
Rate (kg/ha)
Species 1.0 1.0 1.0 1.0
______________________________________
Velvetleaf 100 100 100 100
Barnyardgrass
95 100 95 100
Soybean 85 100 100 95
Morningglory 100 100 100 100
Green foxtail
95 100 100 100
Johnsongrass 95 100 100 100
Wheat 90 95 95 95
Corn 100 95 100 100
Cotton 100 100 100 100
Rice 80 80 80 90
Wild mustard 95 95 100 95
______________________________________
Compound No.
53 54 55 56
Rate (kg/ha)
Species 1.0 1.0 1.0 1.0
______________________________________
Velvetleaf 100 100 100 100
Barnyardgrass
100 70 90 70
Soybean 100 100 95 100
Morningglory 100 100 100 100
Green foxtail
100 70 100 100
Johnsongrass 100 50 100 100
Wheat 100 90 95 95
Corn 100 70 100 100
Cotton 100 100 100 100
Rice 100 70 100 95
Wild mustard 100 100 95 100
______________________________________
Compound No.
57 58 59 60
Rate (kg/ha)
Species 1.0 1.0 1.0 1.0
______________________________________
Velvetleaf 100 100 100 100
Barnyardgrass
10 95 50 100
Soybean 70 100 95 100
Morningglory 30 100 100 100
Green foxtail
30 100 100 100
Johnsongrass 20 100 100 100
Wheat 40 100 85
Corn 40 95 90 90
Cotton 100 100 100 100
Rice 15 85 90 80
Wild mustard 50 100 100 100
______________________________________
Compound No.
61 62 63 64
Rate (kg/ha)
Species 1.0 1.0 1.0 1.0
______________________________________
Velvetleaf 100 100 100 100
Barnyardgrass
95 95 100 100
Soybean 95 100 100 100
Morningglory 100 100 100 100
Green foxtail
100 100 100 100
Johnsongrass 100 100 100 100
Wheat 100 95 100 100
Corn 95 95 100 100
Cotton 100 100 95 95
Rice 95 95 100 100
Wild mustard 100 100 100 85
______________________________________
Compound No.
65 66 67 68
Rate (kg/ha)
Species 1.0 0.5 1.0 1.0
______________________________________
Velvetleaf 100 100 100 100
Barnyardgrass
100 100 95 95
Soybean 95 100 95 95
Morningglory 100 100 95 100
Green foxtail
100 100 100 100
Johnsongrass 100 -- 95 100
Wheat 100 100 100 100
Corn 90 80 95 90
Cotton 100 90 100 100
Rice 90 85 95 90
Wild mustard 100 95 100 100
______________________________________
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